Certain oxyalkylated glucoses and method of making same



July 12, 1960 M. DE GROOTE ETAL 2,945,024

CERTAIN OXYALKYLATED GLUCOSES AND METHOD OF MAKING SAME Original Filed May 24, 1954 BUTY LENE OXIDE I00 7.

GLUCOSE ETHYLENE OXIDE w CERTAIN OXYALKYLATED GLUCOSES AND METHOD OF MAKMG SANE Melvin De Groote, St. Louis, and Owen H. Pettingill, Kirkwood, Mo., assignors to Petrolite Corporation, Wilmington, Del., a corporation of Delaware Original application May 24, 1954, Ser. No. 431,789. Divided and this application Apr. 17, 1957, Ser. No. 653,447 a 7 Claims. or. 260-209) This application is a division of our copending application Serial No. 431,789, filed May 24,1954.

Our invention is concerned with new chemical products or compounds useful as demulsifying agents in processes or procedures particularly adapted for preventing, breaking or resolving emulsions of the water-in-oil type and particularly petroleum emulsions. Our invention is also concerned with the application of such chemical prod-. ucts or compounds in various other arts and industries as well as with methods of manufacturing the new chemical products or compounds which are of outstanding value in demulsification.

More specifically then, the present invention is concerned wtih a cogeneric mixture of a homologous series of glycol ethers of glucose. The cogeneric mixture is derived exclusively from glucose, ethylene oxide and butylene oxide in such weight proportions so the average composition of saidcogeneric mixture statedin terms of initial reactants lies approximately within the -sided figure of the accompanying drawing in which the minimum glucose content is at least 1.5% and which S-sided figure is identified by the fact that its area lies within the straight lines connecting A, B, C, D, and H. i

We have found that when glucose is combined with butylene oxide and ethylene oxide in certain proportions and particularly when the butylene oxide is employed first, followed by use of ethylene oxide and more especially if the butylene oxide employed is one of the straight chain isomers or a mixture of the two, and if the composition falls within the limits indicated by the 5-si'ded figure on the hereto attached triangular chart, said derivatives are of ,in the resolution of petroleum emulsions of the water-inoil type.

In a general way the compounds which have been found 2,45,024 Patented, .iniy 7.2, 1960 most effective and fall within the limits of the chart are combinations where one part of glucose has been treated with about 11 to 39 parts of butyleneoxide, by weight, and then reacted with 27 to 58.5 parts of ethylene oxide.

In another series 10 parts of glucose have been reacted with 5 parts. by weight of butylene oxide and 85 parts by weight of ethylene oxide. In another series 1.5 parts by weight of glucose have been reacted with 13,5 parts by weight of butylene oxide and 85 parts byweight of ethylene oxide. Similarly, in another series the following combinations, have been used: 1.5 parts of glucose combined with 58.5 parts by weight of butylene oxide and 40 parts by weight of ethylene oxide; 20 parts by weight of glucose, reacted with 40 parts by weight of butylene oxide and then with 40 parts by weight of ethylene oxide; In another series 20 parts by weight of glucose were reacted with 10 parts, by weight of butylene oxide and then parts by weight of ethylene oxide.

It is of interest to note in some instances as little. as

1.5 parts of glucose may be combined with 98.5 parts of the two oxides to produce very valuable derivatives.

We have also found that where part of the butylene oxide is replaced by propylene oxide, i.e., where a combination of glucose, butylene oxide, propylene oxide and ethylene oxide are used, effective and valuable surfaceactive agents can also be obtained. This, however, represeats a separate invention. 1

The products of the present invention are also useful for various purposes other than the resolution of petrole; um emulsions of the water-in-oil type. 7 '7 The new products are useful as wetting, detergent and leveling agents in the laundry, textile and dyeing industries; as wetting agents and detergents inthe acid washing of building stone and brick; as wetting agents and spread,- ers in the application of asphalt in road building and the like; as a flotation reagent in the flotation separationof various aqueous suspensions containing negatively charged particles, such as sewage, coal washing waste water, and various trade wastes and the like; as germicides, insecticides, emulsifying agents as, for example, for cosmetics, spray oils, water-repellent textile finishes; as lubricants, etc.

For the purpose of resolving petroleum emulsions of the water-in-oil type, and also for that matter for numerous other purposes where surface-active materials are elfective, and particularly for those uses specified else,- where herein, we prefer to employ oxyalkylated derivatives, which are obtained by the use of .monoepoxides, in such manner that the derivatives so obtained have sufficient hydrophile character to meet at least the test set forth in U.S. Patent No. 2,499,368, dated March 7, 1950, to De Groote and Kaiser. In said patent such test for emulsification using a water-insoluble solvent, generally For purpose of convenience what is said hereinafter will be divided into four parts:

Part 1 is concerned with the oxyalkylation of glucose in general;

Part 2 is concerned with the oxy-alkylation of glucoseusing two difierent oxides, i.e., butylene oxide and ethylene oxide so as to produce derivatives falling within certain composition limitations hereinafter noted in detail. For convenience, Part 2 is divided into two sections, Section A is concerned with oxybutylation and oxyethylation broadly, and Section B is concerned with the particular compositions correspondingto the herein specified compositions and illustrate Such combinations;

Part 3 is concerned with the resolution of petroleum emulsions of the water-in-oil type by means of the previously described chemical compounds; and

Part 4 is concerned with uses for the products herein described either as such or after modification, including applications other than those involving the resolution of petroleum emulsions of the water-in-oil type.

PARTI At the present time there is available butylene oxide which includes isomeric mixtures, for instance, one manufacturer has previously supplied a mixed butylene oxide which is in essence a mixture of l-butene oxide, Z-butene oxide isomers and approximately isobutylene oxide. Another manufacturer has supplied an oxide which is roughly a fifty-fifty mixture of the cisand trans-isomers of Z-butene oxide. 2

There is also available a butylene oxide which is characterized as straight chain isomers being a mixture of the 1,2 and the 2,3 isomers and substantially free from the isobutylene oxide.

This latter product appears to consist of 80% of the 1,2 isomer and of the mixed 2,3 cisand 2,3 transisomer. We have obtained the best results by using an oxide that is roughly 80% or more of the 1,2 isomer and with either none, or just a few percent if any, of the isobutylene oxide, the difference being either form of the 2,3 or a mixture of the two forms.

Our preference is to use an oxide substantially free from the isobutylene oxide, or at least having minimum amounts of isobutylene oxide present.

Since the varying solubility of different butanols is well known, it is unnecessary to comment on the effect that the varying structure has on solubility of derivatives obtained by butylene oxide. Purely by way of example, the applicants have tested the solubility of the first two available butylene oxides and noted in one instance the butylene oxide would dissolve to the extent of 23 grams in 100 grams of water, whereas the other butylene oxide would only dissolve to the extent of 6 grams in 100 grams of water. These tests were made at 25? C.

As to further reference in regard to the isomeric butylene oxide see Chemistry of Carbon Compounds, volume I, Part A, Aliphatic Compounds, edited by E. H. Rood, Elsevier Publishing Company, New York, 1951, page 671. i

' As to the difference in certain proportions of the cisand trans-form of straight chain isomers 2,3-epoxybutane see page341 of A Manual of Organic Chemistry, volume l, G. Malcolm Dyson, Longmans, Green and Company, New York, 1950.

Reference to butylene oxide herein of course is to the compound or compounds having the oxirane ring and thus excludes 1,4-butylene oxide (tetrahydrofurane) or a trimethylene ring compound.

. When reference is made to the oxides, for instance,

ethylene oxide and butylene oxide, one can use the corresponding carbonates.

Ethylene carbonate is available commercially. Butylene carbonate, or the carbonate corresponding to a particular oxide, is not available commercially but can be prepared by the usual methods in the laboratory. For this reason further reference to the alkylene carbonates will be ignored although it is understood when oxyethylation takes place by means of ethylene carbonate one could, of course, use butylene carbonate for oxybutylation.

In the present invention we have found that outstanding products are obtained by the use of certain preferred butylene oxides, i.e., those entirely free or substantially free (usually 1% or less) and composed of approximately or more of the 1,2 isomer with the remainder, if any, being the 2,3 isomer.

In the preparation of the outstanding compounds we have studiously avoided the presence of the isobutylene oxide as far as practical. When any significant amount of isobutylene oxide happens to be present, the results are not as satisfactory regardless of the point when the butylene oxide is introduced. One explanation may be the following. The initial oxybutylation which may be simplified by reference to a monohydric alcohol, produces a tertiary alcohol. Thus the oxybutylation in the presence of an alkaline catalyst may be shown thus:

ROC-C H Further oxyalkylation becomes difiicult when a tertiary alcohol is involved although the literature records successful oxyalkylation of tertiary alcohols. This does not necessarily apply when oxyalkylation takes place in the presence of an acidic catalyst, for instance, a metallic chloride such as ferric chloride, stannic chloride, aluminum chloride, etc. e

. The difficulty is that there may be some tendency on the part of glucose to decompose. The decomposition products probably are still hydroxylated in part and if it does happen to occur oxyalkylation would then involve glucose and hydroxyl containing glucose composition products. We have tried procedures using an alkaline catalyst. and glucose employing 4 to 6 moles of isobutylene oxide per mole of glucose. Afterwards an amount of acid was added equal to the amount of caustic employed as a catalyst and the reaction mass dried and then stannic chloride added. Under such circumstances the results suggest more satisfactory oxybutylation as such although the procedure becomes cumbersome, uneconomical and perhaps even impractical.

This, however, seems to be only a partial explanation. Another explanation may rest with the fact that isobutylene oxide may show a .tendency to revert back to isobutylene and oxygen and this oxygen may tend to oxidize the terminal hydroxyl radicals. This possibility is purely a matter of speculation, but may account for the reason we obtain much better results using a butylene oxide as specified. In regard to this reaction, i.e., possible conversion of an alkylene oxide back to the olefine and nascent oxygen, see Tall Oil Studies II. Decolorization of Polyethenoxy Tallates with Ozone and Hydrogen Peroxide, J. V. Karabinos et al., J. Am. Oil Chem. Soc. 31, 71 (1954).

In order to illustrate why the herein contemplated compounds or said products are cogeneric mixtures and not single chemical compounds, and why they must be described in terms of manufacture, and molal ratio or percentage ratio of reactants, reference is made to a really producing a polymer of the alkylene oxide except for the terminal group. This is particularly true where the amount of oxide added is comparatively large, for instance, 10, 20, 30, 40, or 50 units. If such a compound is subjected to oxyethylation so as to introduce 30 units of ethylene oxide, it is well known that one does not obtain a single constituent which, for sake of convenience, may. beindicated as RO(C H O)3oH. Instead, one obtains a cogeneric mixture of closely related homologues in which the formula ,may be shown as the following: RO(C H O) T, wherein n, as far as the statistical average goes, is 30, but the individual members present in significant amount may vary from instances where n has a value of 25 and perhapsless, to a point where It may represent 35 or more. Such mixture is, as stated, a cogeneric closely related series of touching homologous compounds. Considerable investigation has been made in regard to the distribution curves for linear polymers. Attention is directed to the article entitled Fundamental Principles of Condensation Polymerization, by Paul J. Flory, which appeared in Chemical Reviews, volume 39, No. 1, page 137.

Unfortunately, as has been pointed out by Flory and other investigators, there is no satisfactory method, based on either experimental or mathematical examination of indicating the exact proportion of the various members of touching homologous series which appear in cogeneric condensation products of the kind described. This means that from the practical standpoint, i.e., the ability to describe how. to make the product under consideration and how to repeat .such production time after time without difficulty, it is necessary to resort to some other method of description.

, oxide.

PART 2 Section A We have found that we can oxybutylate glucose in the same manner that it is used conventionally for the oxypropylation. For example, we have followed the directions which appear in columns 4, 5, 6, 7 and 8 of US. Patent No. 2,626,935, dated January 27, 1953, to De Groote in regard to the oxypropylation of glucose and substituting butylene oxide for propylene oxide in action as set forth in Examples 1a through 4a, inclusive. Stirrer speed, temperature, time period, amount of solvent used, amount of catalyst used, and operating pressure glucose. Actually the procedure is substantially the same whether one uses propylene, ethylene, or butylene oxide.

mately 150 C. At this particular time the addition of butylene oxide was started. The butylene oxide employed was a mixture of the straight chain isomer substantially free from isobutylene oxide. It was added continuously at such speed that it was absorbed by the reaction as added. The amount added in this operation was 1500 grams. The time requiredto add the butylene oxide was two hours. 7 During this period the temperature was maintained at 135 to 150 C,, using cooling water through the inner coils when necessary and otherwise applying heat if required. The maximum pressure during the reaction was pounds per square inch. Ignoring the xylene and sodium methylate and considering the glucose for convenience, the resultant product represents 3 parts by weight of butylene oxide to one part by weight of glucose. The xylene present represented approximately .6 of one part by weight.

Example 2a Example 3a Y In a third step, instead of adding 1500 grams of butylene oxide, 1625 grams were added. The reaction slowed up and required approximately 6 hours, using the same operating temperatures and pressures. The ratio at the end of the third step was 9.25 parts by weight of butylene oxide per weight of glucose.

Example 4a At the end of this step the autoclave was opened and an additional 5 grams of sodium methylate added, the autoclave flushed out as before, and the fourth and final oxyalkylation completed, using 1625 grams of butylene oxide, and the oxyalkylation was complete within 3% hours using the same temperature range and pressure as previously. At the end of the reaction the product represented approximately 12.5 parts of butylene oxide by weight to one part of glucose.

All the examples, except the first step, were substantially water-insoluble and xylene-soluble.

As'has been pointed out previously these oxybutylated glucose were subjected to oxyethylation in the same manner described in respect to the oxypropylated glucose in identically the same way. We have completed the aforementioned Patent No. 2,626,935. Indeed, the

" procedure is comparatively simple for the reason that "one is working with a liquid and also that ethylene oxide is more reactive than butylene oxide. As a result, using the "same amount of catalyst one can oxyethylate more It is not believed any examples are necessary to illustrate a such well known procedure ,but for purpose of illustration the following are included:

Example 1a The reaction vessel employed was a stainless steel autoclave with the usual devices for heating, heat control,

sodium methylate. The autoclave was sealed, swept with nitrogen gas and stirring started immediately and heat applied. Temperature was allowed to rise to approxirapidlythan usually at a lower pressure.

There is no substantial diflerence as far as operating procedure goes whether one is oxyethylating oxypropylated glucose or a0 oxybutylated glucose.

The same procedure using a slurry of finely powdered H glucose in xylene was employed in connection with ethylene oxide and the same mixture on a percentage basis was obtained as in the above examples where butylene oxide and glucose were used.

7 The same procedures have been employed using other "butylene oxides including mixtures having considerable land then the other.

In the preceding procedures one oxide has been added One need not follow this procedure. The two oxides can be mixed together in suitable proportions and subsequently subjected to joint oxyalkylation so as to obtain products coming within the specified limits. In such instances, of course, the oxyalkylation may be described as random oxyalkylation insofar that one cannot determine the exact location of the butylene oxide or ethylene oxide groups. In such instances the procedure again is identically the same as previously described and, as a matter of fact, we have used such methods in-connection with molten sorbitol, and als in connection with glucose.

If desired, one may add part of one oxide and all of the other and then return to the use of the first oxide, for instance; or one may usethe procedure as previously, adding first some butylene oxide, then ethylene oxide and then the butylene oxide. Or, inversely, one may add some ethylene oxide, then all butylene oxide and then the remainder of the ethylene oxide; or either oxide could be added in portions so that first one oxide is added, then the other, then the first oxide is added again, and then the second oxide. We have found no advantage in so doing. Indeed, our preference has been to add all the butylene oxide first and then the required amount of ethylene oxide. a

As pointed out previously, glucose can be oxyethylated in the same way it is oxybutylated, i.e., by preparing a slurry in xylene or in a similar solvent and using a suitable alkaline catalyst such as caustic soda, sodium methylate, or the like, and then adding the ethylene oxide. The changes, previously mentioned are of difference in degree only. In other words, oxyethylation will take place at a lower temperature, for instance, a top temperature of probably 130 to l35 C. instead of 145 to 150 C. The same weight of ethylene oxide could be added in 75% to 85% of the time required for butylene oxide. The pressure during the reaction, instead of being 35 to 45 pounds as in the case of butylene oxide, is apt and adding the powdered glucose slowly permits the production of a reaction mass which is a liquid or which melts readily at comparatively low temperatures to yield a liquid. Such reaction should be conducted in such a way that there is no residual ethylene carbonate or for that matter propylene carbonate 'whenthe mass is trans- .ferred to an autoclave. In fact, propylene carbonate is more satisfactory than ethylene carbonate; One can oxyalkylate using an acid catalyst or.- an alkaline catalyst or at least in part,,without the use of any catalyst although such procedure is extremely slow and uneconomical. In other words, anyone of the conventional catalysts used in oxyalkylation may be employed. It is our preference, however, to use an alkalinecatalyst such as sodium methylate, caustic soda, or the like. 7 I T Actually, finely powdered glucose may contain a trace of moisture. Our preference is to prepare the slurry with an excess of xylene and distill off one part of the xylene so as to remove any trace of water and then flush out the mass With nitrogen. Even so, there may be'a few tenths of a percent of moisture remain although at times examination indicates at the most it is merely a trace.

. Section B e In light of what has been said previously, particularly in Section A, it is obvious that hardly any directions are required to produce the compounds herein specified.

However, referring to the composition of the initial reactants based on the 5-sided figure in the attached drawing, it will be noted we have calculated the percentage of the three initial reactants for the points A, B, C, D, E, F, G, H, I and I which appear on the boundary of the S-sided figure and also determine the five subdivided parts of the S-Sidedfigure, two partsbeing triangles and the others being two parallelograms and one trapezoid.

Likewise, We have'calculated the composition for a number of examples. within the area of the graph and corresponding to points 1 to 18, inclusive. Note these data 7 are included in Table I, immediately following:

TAIBLIJ r Tertiary Mixture, Binary Intermediate Mixtures, Points on Percent Basis Percent Basis Boundary of Area Glucose Butylene Ethylene Glucose Butylene Glucose Ethylene Oxide Oxide Oxide Oxide 10. 0 5. 0 85.0 66. 6 33. 4 10. 5 89. 5 1. 5 13. 5 85. 0 10. 0 90. 0 1. 7 98. 3 1. 5 58. 5 40. (l 2. 5 97. 5 3. 6 96. 4 20.0 40. 0 40.0 33. 4 66. 6 33. 4 66. 6 1. 5 40. 0 58. 5 3. 6 96. 4 2. 5 97. 5 1. 5 30. 0 68. 5 4. 95. 25 2. 14 97.86 1. 5 20.0 78. 5 7. 0 93.0 1. 87 98. 13 20. 9 10.0 70. 0 66. 6 33. 4 22. 2 77. 8 20.0 20. 0 60.0 50.0 50. 0 25. 0 75.0 20.0 30. 0 50. 0 40.0 60.0 28. 6 71. 4 5. 0 52. 5 42. 5 8. 68 91. 32 10. 5 89.5 8.0 44. 0 48.0 15. 4 84. 5 14. 3 85.7 p 1. 5 54. 5 44. 0 2. 68 97. 32 3. 3 96. 7 18.0 36. 5 45. 5 33. 0 67. 0 28. 3 71. 7 15. 0. 33. 5 51. 5 31.0 69.0 22. 6 77.4 7. 5 36. 5 56. 0 17. 1 82.9 11. 8 88. 2 1. 5 34. 5 64. 0 V 4. 16 95. 84 2. 3 97. 7 17.0 28. O 55.0 37. 7 62.8 23. 6 '76. 4 7. 0 26. 0 67. 0 21. 2 78. 8 9. 5 90. 5 13. 5 22. 5 64. 0 37. 5 62. 5 l7. 4 '82. 6 15. 5 19. 0 65. 5 44. 8 55. 2 19. 2 80. 8

4. 5 23. O 72. 5 16. 35 83. 65 5. 94. 15 6. O 17.0 77. 0 26. 1 73. 9 7. 2 92. 8 1. 5 17.0 81. 5 8. 1 91. 9 1. 8 98. 2 16. O 12. 5 71. 5 56. 2 43. 8 18. 3 81. 7 4. 5 13.0 82. 5 25. 7 74. 3 5. 2 94. 8 13. 5 9. 0 77. 5 60.0 40.0 14. 8 85. 2 11. 5 7.0 81. 5 62. 1 37.9 12. 35 87. 65

Otherwise, there is no difference.

Also, if desired, the use of ethylene carbonate is a very convenient way of oxyethylating glucose. In fact,

it can be oxyethylated without the use of pressure. Such figure. 'tiary mixture which corresponds to the initial reactants, to wit, the percentages, by weight, of glucose, butylene to be 10 to 15 pounds and at times a little higher. 76 Note the first columnpgives the particular point on the boundary of the 5-sided figure or within the 5-sided Note the next three columns represent the terpr'ocedure, and particularly melting the carbonate first 1T5 oxide and ethylene oxide. Thus it is apparent that one Note the fifth and sixth columns represent binary intermediate mixtures. For instance, in regard to the various points on the boundary and within the S-sided figure, We have calculated the initial mixture using glucose and butylene oxide in the first case, and using glucose and ethylene oxide in the second case, which would'be employed for subsequent oxyalkylation to give the particular composition required. Note that a binary intermediate for the preparation of point A can be prepared in any suitable manner involving 66.6% of glucose and 33.4% of butylene oxide. Thus, for example one could use 66.6 pounds of glucose and 33.4 pounds of butylene oxide, or on a larger scale one could use 666 pounds of glucose and 334 pounds of butylene oxide.

Referring now to the tertiary mixture table, it is apparcut that for point A glucose and butylene oxide together represent 15%, and ethylene oxide 85%. Therefore, one could employ 1 pounds of the binary mixture and react it with 85 pounds of ethylene oxide.

Similarly, in regard to the fifth and sixth columns for point B, the initial mixture involved glucose and butylene oxide, representing 10% .of glucose and 90% of butylene oxide. If desired 10 pounds of glucose could be reacted with 90 pounds of butylene oxide. Such mixture need only be reacted with ethylene oxide by reacting pounds of the mixture with 85 pounds of ethylene oxide. This is obvious from the data in regard to the tertiary m xtures.

Referring now to columns 7 and 8, it is obvious one could readily produce an oxyethylated glucose andthen subject it to reaction with butylene oxide. Using this procedure in regard to A, it is obvious that the mixture represents 10.5% of glucose and 89.5% of ethylene oxide.

This product could be obtained from a binary mixture of 105 pounds of glucose and 895 pounds of ethylene oxide.

Referring now to the tertiary mixture table, it is obvious that 95 pounds of such mixture could be reacted with 5 pounds of butylene oxide to give point A. Similarly, in regard to point B the oxyethylated glucose represents 1.7% of glucose and 98.3% ethylene oxide. The mixture so obtained by referring to the tertiary mixture table would be reacted with butylene oxide in the proportion of 86.5 pounds of the mixture and 13.5 pounds of butylene oxide.

As previously pointed out, the oxyalkylation of glucose has been described in the literature and is described also in detail above. All one need do is employ such con- Ventional oxyalkylation procedure to obtain products corresponding to the compositions as defined. Attention is again directed to the fact that one need not add the entire amount of either oxide at one time but that a small portion of one could be added and then another small portion of the other, and the process repeated.

Purely for purpose of illustration, we have prepared examples three diiferent ways corresponding to the compositions shown on the chart. In the first series the butylene oxides and ethylene oxide were mixed; this series is indicated as Aa, Ba, through and including 18a; in the second series butylene oxide was used first followed by ethylene oxide and this series indicated Ab, Eb, through and including 1812; and finally in the third series ethylene oxide was used followed by butylene oxide and the series identified as Ac, Bc, through and including 180.

TABLE II Composition Composition Composition where Butylwhere Ethyl Composition Corresponding where Oxides ene Oxide ene Oxide to Following Point are Mixed Used First Used First Prior to Oxy- Followed by Followed by alkylation Ethylene Butylene Oxide Oxide Ba Bb Bc Ca Cb Cc De Db Dc Ea Eb Ec Fu- Fb Fe Ga Gb Gc Ha Hb Hc la II) To J'a I b Is la 1b 10 10a 10b 10c lla 11b 11c 14a 14b 14a I 17a 17b 17c The products obtained by the above procedure usually show some color varying from a light amber to a pale straw. They can be bleached in the usual fashion using bleaching clays, charcoal, or an organic bleach, such as peroxide or peracetic acid, or the like.

Such products alsohave present a small amount of alkaline catalyst which can be removed by conventional means, or they can be neutralized by adding an equivalent amount of acid, such as hydrochloric acid. For many purposes the slight amount of residual alkalinity is not objectionable.

There are certain variants which can be employed without detracting from the metes and bounds of the invention, but for all practical purposes there is nothing to be gained by such variants and the result is merely increased cost. For instance, any one of the two oxides can be replaced to a minor percentage and usually to a very small degree, by oxide which would introduce substantially the same group along with a side chain, for instance, one could employ glycidyl methyl ether, glycidyl ethyl ether, glycidyl isopropyl ether, glycidyl butyl ether or the like.

In the hereto appended claims reference has been made to glycol ethers of glucose. Actually it well may be that the products should be referred to as polyol ethers of glucose in order to emphasize the fact that the final products of reaction have more than two hydroxyl radicals. However, the product may be considered as hypothetically derived by reaction of glucose with the glycols, such as ethylene glycol, butylene glycol, propylene glycol, or polyglycols. For this reason there seems to be a preference to use the terminology glycol ethers of glucose.

PART 3 As to the use of conventional demulsifying agents, reference is made to U.S. Patent No. 2,626,929, dated January 7, 1953, to De Groote, and particularly to Part 3. Everything that appears therein applies with equal force and effect to the instant process, noting only that where reference is made to Example 13b in said text beginning in column 15 and ending in column 18, reference should be to Example 18b, herein described.

PART 4 The compounds derived in the manner described may be used as such for breaking petroleum emulsions of the water-in-oil type. They also can be converted into derivatives of the kind subsequently described which also may be used for this same purpose. Such derivatives are use: ful ,for other purposes including the same purpose for which the herein describedproducts are efiective. The herein described products may be used for various purposes where detergents, c ommon solvents, emulsifiers, and the like are used. They may be used as lubricants and as additives to fluids used in hydraulic brake systems: they may be usedas emulsifying agents to emulsify to remove greases or dirt; they may be used in; the manutacture of a variety of other materials such as soluble oils, insecticide sprays, etc. 7 V 1 These products may be combined with avariety of reactants as chemical intermediates, for instance, with various diepoxides or polyepoxides. They may be combined with a number of other monoepoxides, such as epichlorohydrin styrene, oxide, glycide and methylglycide. They may be reacted with allyl glycidyl ether, glycidylisopropyl ether, and glycidyl phenyl ether.

Furthermore, such products may be reacted with alkylene imines, such as ethylene imine or propylene imine, to produce cation-active materials. Instead of an imine, one

may employ what is a somewhat equivalent. materi aL to wit a dialkylaminoepoxypropane of the structure j lubricating oils which are derived from sources other than petroleum. Y

The herein described products and the derivatives thereof are particularly valuable in flooding processes for recovery of oil from subterranean oil-bearing strata when employed in the manner described in U.S. Patent 2,233,381, dated February 25, 1941, to De Groote and K i i I a j a Havingfthus described our invention, what we claim as new and desire to secure by Letters Patent is:

1. A cogeneric mixture of a homologous series of glycol; ethers of 'glucose; said cogeneric mixture being derived exclusively from glucose, ethylene oxide and butylene oxide in such weight proportions so the average composition of said cogeneric mixture, stated in terms of initial reactants, lies approximately within the S-sided figure of the accompanying drawing in which the minimum glucose content is at least 1.5% and which S-sided figure is identified by the fact that its area lies within the straight lines connecting A, B, C, D, and H. 2. The cogeneric mixture of claim 1 with the proviso that the reactant composition falls within the triangular area defined by C, D, and E.

3. The cogeneric mixture of claim 1 with the proviso that the reactant composition falls within the parallelogram D, E, F, and J. a I 1 4. The cogeneric mixture of claim 1 with the proviso that the reactant composition falls within the pallelogram J, F, G, and I.

5. 'The cogeneric mixture of claim 1 with the proviso that the reactant composition falls within the trapezoid I, G, B, and H.

6. The cogeneric m xture of claim 1 with the proviso that the reactant composition falls within the triangle I-I, B, A. t p 7. The co'generic mixture of claim 1 wherein the butylene oxide is a straight chain butylene oxide and wherein the oxybutylene radicals are linked to the glucose.

' References Cited in the file of this patent V UNITED STATES PATENTS OTHER REFERENCES I Pigman et al.: Chemistry of the Carbohydrates, 1948, publ. by Academic Press Inc. (New York), page 556. 

1. A COGENERIC MIXTURE OF A HOMOLOGOUS SERIES OF GLYCOL ETHERS OF GLUCOSE, SAID COGENERIC MIXTURE BEING DERIVED EXCLUSIVELY FROM GLUCOSE, ETHYLENE OXIDE AND BUTYLENE OXIDE IN SUCH WEIGHT PROPORTIONS SO THE AVERAGE COMPOSITION OF SAID COGENERIC MIXTURE, STATED IN TERMS OF INITIAL REACTANTS, LIES APPROXIMATELY WITHIN THE 5-SIDED FIGURE OF THE ACCOMPANYING DRAWING IN WHICH THE MINIMUM GLUCOSE CONTENT IS AT LEAST 1.5% AND WHICH 5-SIDE FIGURE IS IDENTIFIED BY THE FACT THAT ITS AREA LIES WITHIN THE STRAIGHT LINES CONNECTING A,B,C,D, AND H. 